KR20230153390A - Resin composition - Google Patents

Abstract

The object of the present invention is to provide a resin composition that can lower the dielectric loss tangent, suppress the occurrence of cracks after desmear treatment, and obtain a cured product with excellent copper plating peel strength. The present invention is a resin composition comprising (A) an epoxy resin and (B) an active ester compound, wherein component (A) is (A-1) represented by the formula (1) and has an epoxy equivalent of 1,000 g/eq. to 5,000 g/eq. of epoxy resin and (A-2) epoxy equivalent weight of 200 g/eq. It is a resin composition containing the following epoxy resin. The definition of each symbol in Formula 1 is as described in the specification.

Description

Resin composition

The present invention relates to a resin composition containing an epoxy resin. It also relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method using the build-up method, generally, the insulating layer is formed by curing the resin composition. Recently, there has been a demand for further improvement in dielectric properties such as dielectric constant of the insulating layer and further improvement in copper adhesion. However, until now, when materials with high copper plating peel strength were used, there were problems with the minimum melt viscosity of the resin composition and the size of the dielectric loss tangent (Df) of the material.

Until now, it has been known that the dielectric loss tangent of the insulating layer can be suppressed to a lower level by using an epoxy resin composition containing an active ester compound instead of a general phenol-based curing agent as a resin composition for forming the insulating layer (patent Document 1).

Japanese Patent Publication No. 2020-23714 Japanese Patent Publication No. 2016-89165

However, when an active ester compound is used, the dielectric loss tangent can be suppressed to a lower level, but cracks tend to occur easily after desmear treatment. Additionally, characteristic epoxy resins have been known so far (Patent Document 2).

The object of the present invention is to provide a resin composition that can suppress the dielectric loss tangent to a lower level, suppress the occurrence of cracks after desmear treatment, and obtain a cured product with excellent copper plating peel strength.

In order to achieve the object of the present invention, the present inventors have intensively studied and found that (B) an epoxy resin composition containing an active ester compound, (A-1) an epoxy resin composition represented by the formula (1) described below. Equivalent weight is 1,000g/eq. to 5,000 g/eq. of epoxy resin and (A-2) epoxy equivalent weight of 200 g/eq. By using the following epoxy resin, it was surprisingly discovered that the dielectric loss tangent could be suppressed to a lower level, the occurrence of cracks after desmear treatment could be suppressed, and a cured product with excellent copper plating peel strength could be obtained. The present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin and (B) an active ester compound,

(A) The component is,

(A-1) Formula 1:

[Formula 1]

[In Formula 1,

Each R ¹ independently represents a hydrogen atom, an alkyl-carbonyl group which may have a substituent, an alkenyl-carbonyl group which may have a substituent, or an aryl-carbonyl group which may have a substituent, and at least one of R ¹ The above are groups selected from alkyl-carbonyl groups which may have a substituent, alkenyl-carbonyl groups which may have a substituent, and aryl-carbonyl groups which may have a substituent;

Ar is each independently, Formula X:

[Formula X]

(In formula

R ² and R ³ each independently represent a substituent;

X represents a single bond or an organic group;

a and b each independently represent 0, 1, 2, 3, or 4;

* indicates binding site)

Represents a group represented by;

n is an integer greater than or equal to 1 and represents the number of repeat units]

The epoxy equivalent weight, expressed as 1,000 g/eq. to 5,000 g/eq. of epoxy resin and

(A-2) Epoxy equivalent weight is 200g/eq. A resin composition containing the following epoxy resin.

[2］Ar each independently, Formula X-1:

[Formula X-1]

(In Formula X-1,

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group;

X ¹ represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;

R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;

* indicates binding site)

A group represented by or formula X-2:

[Formula X-2]

(In Formula X-2,

X ² represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;

R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;

* indicates binding site)

The resin composition according to [1], which is a group represented by , and also contains at least one group Ar represented by the formula X-1 and Ar represented by the formula X-2.

[3] The resin composition according to [2] above, wherein X ¹ and X ² are single bonds.

[4] The resin composition according to any one of [1] to [3] above, wherein the content of the component (A-1) is 3% by mass to 20% by mass when the component (A) is 100% by mass.

[5] Any of the above [1] to [4], wherein the mass ratio of the (A-1) component to the (A-2) component ((A-1) component/(A-2) component) is 0.01 to 1. The resin composition described in one.

[6] The resin composition according to any one of [1] to [5] above, wherein the content of component (A) is 1% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass.

[7] The resin composition according to any one of [1] to [6] above, wherein the content of component (B) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[8] The resin composition according to any one of [1] to [7] above, wherein the mass ratio of component (B) to component (A) (component (B)/component (A)) is 0.5 to 3.0.

[9] (C) The resin composition according to any one of [1] to [8] above, further comprising an inorganic filler.

[10] The resin composition according to [9] above, wherein the component (C) is silica.

[11] The resin composition according to [9] or [10] above, wherein the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[12] (D) The resin composition according to any one of [1] to [11], further comprising an organic filler.

[13] The resin composition according to [12] above, wherein the (D) component contains core-shell rubber particles.

[14] The resin composition according to any one of [1] to [13] above, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C.

[15] A cured product of the resin composition according to any one of [1] to [14] above.

[16] A sheet-like laminate material containing the resin composition according to any one of [1] to [14] above.

[17] A resin sheet having a support and a resin composition layer formed of the resin composition according to any one of [1] to [14] provided on the support.

[18] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [14] above.

[19] A semiconductor device comprising the printed wiring board according to [18] above.

According to the resin composition of the present invention, the dielectric loss tangent can be suppressed to a lower level, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with excellent copper plating peel strength can be obtained.

Hereinafter, the present invention will be described in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with any modification without departing from the scope of the claims and equivalents of the present invention.

<Resin composition>

The resin composition of the present invention includes (A) an epoxy resin and (B) an active ester compound, and the component (A) is (A-1) represented by the formula (1) described below, and has an epoxy equivalent of 1,000 g/eq. to 5,000 g/eq. (hereinafter sometimes referred to as “specific epoxy resin”) and (A-2) an epoxy equivalent weight of 200 g/eq. It includes the following epoxy resins. By using such a resin composition, the dielectric loss tangent can be suppressed to a lower level, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with excellent copper plating peel strength can be obtained.

The resin composition of the present invention may further contain arbitrary components in addition to (A) the epoxy resin and (B) the active ester compound. Optional components include, for example, (B') other curing agents, (C) inorganic fillers, (D) organic fillers, (E) curing accelerators, (F) other additives, and (G) organic solvents. Hereinafter, each component included in the resin composition will be described in detail.

<(A) Epoxy resin>

The resin composition of the present invention contains (A) an epoxy resin. (A) An epoxy resin is a curable resin having an epoxy group.

<(A-1) Specific epoxy resin>

In the resin composition of the present invention, (A) the epoxy resin is (A-1) Formula 1:

[Formula 1]

[In Formula 1,

R ¹ each independently represents a hydrogen atom, an alkyl-carbonyl group which may have a substituent, an alkenyl-carbonyl group which may have a substituent, or an aryl-carbonyl group which may have a substituent, and at least one of R ¹ The above are groups selected from alkyl-carbonyl groups which may have a substituent, alkenyl-carbonyl groups which may have a substituent, and aryl-carbonyl groups which may have a substituent;

Ar is each independently, Formula X:

[Formula X]

(In formula

R ² and R ³ each independently represent a substituent;

X represents a single bond or an organic group;

a and b each independently represent 0, 1, 2, 3, or 4;

* indicates binding site)

Represents a group represented by;

n is an integer greater than or equal to 1 and represents the number of repeat units]

The epoxy equivalent weight, expressed as 1,000 g/eq. to 5,000 g/eq. of epoxy resin (specified epoxy resin).

R ¹ each independently represents a hydrogen atom, an alkyl-carbonyl group which may have a substituent, an alkenyl-carbonyl group which may have a substituent, or an aryl-carbonyl group which may have a substituent, and at least one of R ¹ The above are groups selected from alkyl-carbonyl groups which may have a substituent, alkenyl-carbonyl groups which may have a substituent, and aryl-carbonyl groups which may have a substituent.

In this specification, the substituent is not particularly limited and includes, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), and an alkyl-aryl group (an aryl group substituted with an alkyl group). ), halogen-substituted alkyl group (alkyl group substituted with a halogen atom), halogen-substituted alkenyl group (alkenyl group substituted with a halogen atom), halogen-substituted aryl group (aryl group substituted with a halogen atom), alkyl-oxy group, alkenyl-oxy group, Aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group , alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, etc., and, if substitutable, it may also include a divalent substituent such as oxo group (=O).

A halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and among these, a fluorine atom is preferable.

Alkyl (group) means a straight-chain, branched-chain and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably an alkyl (group) having 1 to 10 carbon atoms, and an alkyl (group) having 1 to 6 carbon atoms. Alkyl (group) is more preferred. Examples of alkyl (group) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2,4-trimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, etc. I can hear it.

Alkenyl (group) means a straight-chain, branched-chain and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl (group) is preferably alkenyl (group) having 2 to 14 carbon atoms, more preferably alkenyl (group) having 2 to 10 carbon atoms, and 2 carbon atoms. Alkenyl groups of to 6 are more preferable. Examples of alkenyl (group) include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), Pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, cyclohexenyl group, etc. are mentioned.

Aryl (group) means a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom of an aromatic carbocyclic ring. Unless otherwise specified, the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, and an aryl (group) having 6 to 10 carbon atoms is particularly preferable. Examples of aryl (group) include phenyl group, 1-naphthyl group, and 2-naphthyl group.

R ¹ each independently represents a hydrogen atom, an alkyl-carbonyl group which may have a substituent, an alkenyl-carbonyl group which may have a substituent, or an aryl-carbonyl group which may have a substituent, and in one embodiment, it is preferred. Preferably, it is a hydrogen atom, an alkyl-carbonyl group, an alkenyl-carbonyl group, or an aryl-carbonyl group, more preferably, it is a hydrogen atom or an alkyl-carbonyl group, and even more preferably, it is a hydrogen atom, an acetyl group, or a propanoic acid group. It is a diary group, butanoyl group, or 2-methylpropanoyl group, and particularly preferably, it is a hydrogen atom or an acetyl group.

R ¹ is an atom in which at least one is other than a hydrogen atom (i.e., an alkyl-carbonyl group that may have a substituent, an alkenyl-carbonyl group that may have a substituent, and an aryl-carbonyl group that may have a substituent). It is). In one embodiment, R ¹ is preferably at least 5 mol%, more preferably at least 20 mol%, even more preferably at least 40 mol%. Of these, 60 mol% or more or 80 mol% or more are other than hydrogen atoms.

R ² and R ³ each independently represent a substituent, and in one embodiment, are preferably an alkyl group, alkenyl group, aryl group, aryl-alkyl group, alkyl-aryl group, alkyl-oxy group, alkenyl-ox. group or an aryl-oxy group, more preferably an alkyl group, alkenyl group or aryl group, further preferably an alkyl group, and particularly preferably a methyl group.

X represents a single bond or an organic group, and in one embodiment, is preferably a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-, more preferably a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S- or -SO ₂ -, and even more preferably , a single bond, -C(R ^x ) ₂ -, or -O-, and particularly preferably a single bond.

In this specification, the organic group is not particularly limited, but in one embodiment, for example, one or more (e.g., 1 to 100) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. , preferably 1 to 50, particularly preferably 1 to 20, is a divalent group consisting of skeletal atoms, may include a straight chain structure, a branched chain structure and/or a cyclic structure, and does not contain an aromatic ring. It may be a group or a group containing an aromatic ring.

R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R Even if it has, it forms a good non-aromatic ring. In one embodiment, preferably, ^R or two ^R do. More preferably, R ^x is each independently a hydrogen atom, an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group, or two ^R . More preferably, R ^x is each independently a hydrogen atom, an alkyl group, or a halogen-substituted alkyl group.

A non-aromatic ring means a ring other than an aromatic ring that has aromaticity throughout the ring. An aromatic ring having aromaticity throughout the ring means a ring that follows Hückel's law, in which the number of electrons included in the π electron system of the ring is 4p + 2 (p is a natural number). A non-aromatic ring may be a non-aromatic heterocycle or a non-aromatic heterocycle containing only carbon atoms as ring-membering atoms, and may have, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. However, in one embodiment In this case, it is preferable that it is a non-aromatic carbocycle. A non-aromatic ring, a non-aromatic saturated ring consisting of only a single bond may be used, or a non-aromatic unsaturated ring having at least one of a double bond and a triple bond may be used. The non-aromatic ring may be a monocyclic non-aromatic ring, or a polycyclic non-aromatic ring such as a dicyclic, tricyclic, tetracyclic, or pentacyclic ring, or may be a condensed aromatic ring (benzene ring, naphthalene ring). The non-aromatic ring is preferably a non-aromatic ring with 3 to 21 carbon atoms, more preferably a non-aromatic ring with 4 to 17 carbon atoms, and even more preferably a non-aromatic ring with 5 to 14 carbon atoms.

Specific examples of the group represented by -C(R ^x ) ₂ - include formulas x1 to x44:

[In the formula, * represents the binding site]

A group represented by can be mentioned.

a and b each independently represent 0, 1, 2, 3, or 4, and in one embodiment, are preferably 0, 1, 2, or 3, and more preferably are 0, 1, or 2. , particularly preferably 0 or 1.

n is an integer greater than or equal to 1 and represents the number of repeat units. The average value of n is not particularly limited, but from the viewpoint of handling of the resin composition, it is preferably 1 or more, more preferably 5 or more, further preferably 8 or more, especially preferably 10 or more, and the upper limit is: Preferably it is 500 or less, more preferably 300 or less, further preferably 200 or less, and particularly preferably 100 or less.

In one embodiment, Ar is preferably each independently represented by Formula X-1:

[Formula X-1]

(In Formula X-1,

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group;

X ¹ represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;

R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;

* indicates binding site)

A group represented by or formula X-2:

[Formula X-2]

(In Formula X-2,

X ² represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;

R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;

* indicates binding site)

It is a group represented by , and also includes at least one group Ar represented by the formula X-1 and Ar represented by the formula X-2.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group. In one embodiment, preferably, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or an alkyl group, and R ¹¹ , R ¹² , at least one of R ¹³ and R ¹⁴ and at least one of R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently an alkyl group. More preferably, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or an alkyl group, and at least one of R ¹¹ and R ¹² and At least one of R ¹⁵ and R ¹⁶ is each independently an alkyl group. More preferably, R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently an alkyl group, and R ¹³ , R ¹⁴ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or an alkyl group. Particularly preferably, R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently a methyl group, an ethyl group, a propyl group or an isopropyl group, and R ¹³ , R ¹⁴ , R ¹⁷ and R ¹⁸ are each independently, It is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group.

X1 represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-, and in one embodiment, , preferably a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S- or -SO ₂ -, more preferably a single bond, -C(R ^x ) ₂ - or -O-, and particularly preferably a single bond.

X2 represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-, and in one embodiment, , preferably a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S- or -SO ₂ -, more preferably a single bond, -C(R ^x ) ₂ - or -O-, and particularly preferably a single bond.

In one embodiment, the group represented by the formula

[In the formula, * represents the binding site]

It is a group represented by, and especially preferably, it is a group represented by the formula X-1-1.

In one embodiment, the group represented by formula (X-2) is particularly preferably represented by formula (X-2-1):

[Formula X-2-1]

[In the formula, * represents the binding site]

It is a group represented by .

In the above embodiment, Ar includes at least one group Ar represented by the formula X-1 and Ar each represented by the formula X-2. In the above embodiment, the proportion of Ar, which is the group represented by the formula is 20 mol% or more. In the above embodiment, the proportion of Ar, which is the group represented by the formula is 20 mol% or more.

In the repeating unit represented by n, the unit where Ar is a group represented by the formula Although they may be arranged, in one embodiment, it is preferable that they are arranged alternately.

(A-1) The epoxy equivalent weight of a specific epoxy resin is 1,000 g/eq. to 5,000 g/eq., preferably 1,300 g/eq. to 4,000 g/eq., more preferably 1,500 g/eq. to 3,500 g/eq., more preferably 1,700 g/eq. to 3,000 g/eq., particularly preferably 1,800 g/eq. to 2,500 g/eq. Epoxy equivalent is the mass of resin per equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(A-1) The weight average molecular weight (Mw) of the specific epoxy resin is not particularly limited, but in one embodiment, from the viewpoint of handling, etc., it is preferably 100,000 or less, more preferably 50,000 or less, and further. Preferably it is 40,000 or less, and the lower limit thereof may be preferably 1,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(A-1) The number average molecular weight (Mn) of the specific epoxy resin is not particularly limited, but in one embodiment, from the viewpoint of handleability, etc., it is preferably 50,000 or less, more preferably 20,000 or less, and further. It is preferably 15,000 or less, and the lower limit thereof may be preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. The number average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(A-1) The polydispersity (Mw/Mn) of the specific epoxy resin is not particularly limited, but in one embodiment, it is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 5.0. And, it is particularly preferable that it is in the range of 2.0 to 3.0.

(A-1) The specific epoxy resin is not particularly limited, but in one embodiment, for example, one or two or more types of bifunctional epoxy resins corresponding to Ar (biphenol diglycidyl ether and/or bisphenol diglycidyl ether) and one or more diester compounds (biphenol ester and/or bisphenol ester) corresponding to Ar in the presence of a catalyst, if necessary. As a specific method, for example, the method described in Japanese Patent Application Laid-Open No. 2016-89165 or a method similar thereto can be used.

The content of the specific epoxy resin (A-1) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably 10% by mass. Below, more preferably 5 mass% or less, even more preferably 2 mass% or less, particularly preferably 1.5 mass% or less. The lower limit of the content of the specific epoxy resin (A-1) in the resin composition is not particularly limited, but is preferably 100% by mass of the non-volatile component in the resin composition from the viewpoint of more significantly obtaining the desired effect of the present invention. Preferably it is 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, and particularly preferably 0.8 mass% or more.

The content of the specific epoxy resin (A-1) in the (A) epoxy resin is not particularly limited, but when the epoxy resin (A) in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably Preferably it is 30 mass% or less, more preferably 20 mass% or less, even more preferably 15 mass% or less, and particularly preferably 10 mass% or less. The lower limit of the content of the specific epoxy resin (A-1) in the (A) epoxy resin is not particularly limited, but from the viewpoint of more significantly obtaining the desired effect of the present invention, the (A) epoxy resin in the resin composition is 100% by mass. In the case of , it is preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 3 mass% or more, even more preferably 5 mass% or more, and particularly preferably 8 mass% or more.

<(A-2) Epoxy equivalent weight 200g/eq. The following epoxy resins>

In the resin composition of the present invention, the (A) epoxy resin (A-2) has an epoxy equivalent of 200 g/eq. It contains the following epoxy resin.

(A-2) Epoxy equivalent weight is 200g/eq. It is preferable that the following epoxy resins contain epoxy resins having two or more epoxy groups in one molecule. (A-2) Epoxy equivalent weight is 200g/eq. The ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of non-volatile components of the following epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass. It is more than mass%.

(A-2) Epoxy equivalent weight 200g/eq. The following epoxy resins are not particularly limited, but include naphthalene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, trisphenol type epoxy resin, and glycidyl epoxy resin. Ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, glycirol type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexane type epoxy resin, bixylenol type epoxy resin, anthracene type epoxy resin. etc. can be mentioned.

(A-2) Epoxy equivalent weight 200g/eq. Specific examples of the following epoxy resins include “HP4032D” (epoxy equivalent weight: 136 to 148 g/eq.) and “HP4032SS” (epoxy equivalent weight: 144 g/eq.) manufactured by DIC (naphthalene type epoxy resin); “828US” (epoxy equivalent weight 184 to 194 g/eq.), “828EL” (epoxy equivalent weight 184 to 194 g/eq.), “jER828EL” (epoxy equivalent weight 184 to 194 g/eq.), and “825” manufactured by Mitsubishi Chemical Corporation. (Epoxy equivalent weight 170 to 180 g/eq.) (bisphenol A type epoxy resin); “jER807” (epoxy equivalent weight: 160 to 175 g/eq.) and “1750” (epoxy equivalent weight: 156 to 163 g/eq.) manufactured by Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); “jER152” (epoxy equivalent weight 176 to 178 g/eq.) manufactured by Mitsubishi Chemical Corporation (phenol novolac type epoxy resin); “630” (epoxy equivalent weight: 90 to 105 g/eq.) and “604” (epoxy equivalent weight: 110 to 130 g/eq.) manufactured by Mitsubishi Chemical Corporation (glycidylamine type epoxy resin); “ED-523T” (epoxy equivalent weight 140 g/eq.) manufactured by ADEKA (glycirol type epoxy resin); “EP-3950L” (epoxy equivalent weight: 95 g/eq.), “EP-3980S” (epoxy equivalent weight: 115 g/eq.) manufactured by ADEKA (glycidylamine type epoxy resin); “EP-4088S” (epoxy equivalent weight 170 g/eq.) manufactured by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" (epoxy equivalent weight 170 g/eq.) manufactured by Nittetsu Chemical & Materials Chemicals Co. (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (epoxy equivalent weight: 154 g/eq.) manufactured by Nagase Chemtex (glycidyl ester type epoxy resin); “Celoxide 2021P” (epoxy equivalent weight 128 to 133 g/eq.) manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); “ZX1658” (epoxy equivalent weight: 135 g/eq.), “ZX1658GS” (epoxy equivalent weight: 135 g/eq.) manufactured by Nittetsu Chemical & Materials (liquid 1,4-glycidylcyclohexane type epoxy resin); “HP-4700” (epoxy equivalent weight: 160 to 170 g/eq.), “HP-4710” (epoxy equivalent weight: 160 to 180 g/eq.) manufactured by DIC (naphthalene type tetrafunctional epoxy resin); "EPPN-502H" (epoxy equivalent weight 168 g/eq.) manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); “ESN375” (epoxy equivalent weight 170 g/eq.) manufactured by Nittetsu Chemical & Materials (dihydroxynaphthalene type epoxy resin); “YX4000H” (epoxy equivalent weight: 187 to 197 g/eq.) and “YX4000” (epoxy equivalent weight: 180 to 192 g/eq.) manufactured by Mitsubishi Chemical Corporation (bixylenol type epoxy resin); “YL6121HA” (epoxy equivalent weight 170 to 180 g/eq.) manufactured by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); and "YX8800" (epoxy equivalent weight 174 to 183 g/eq.) (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

(A-2) Epoxy equivalent weight 200g/eq. The epoxy equivalent of the following epoxy resin is preferably 190 g/eq. or less, more preferably 180 g/eq. or less, and the lower limit thereof is preferably 80 g/eq. or more, more preferably 100 g/eq. or more, more preferably 120 g/eq. or more, particularly preferably 130 g/eq. It could be more than that. Epoxy equivalent is the mass of resin per equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(A-2) Epoxy equivalent weight 200g/eq. The weight average molecular weight (Mw) of the following epoxy resin is preferably 100 to 5,000, more preferably 200 to 3,000, and still more preferably 250 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(A-2) epoxy equivalent in the resin composition: 200 g/eq. The content of the following epoxy resin is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass. It is % by mass or less, more preferably 20 mass % or less, particularly preferably 15 mass % or less. (A-2) epoxy equivalent in the resin composition: 200 g/eq. The lower limit of the content of the following epoxy resin is not particularly limited, but from the viewpoint of more significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, More preferably 0.5 mass% or more, further preferably 1 mass% or more, even more preferably 3 mass% or more, particularly preferably 5 mass% or more.

(A) Epoxy equivalent weight of (A-2) in epoxy resin: 200 g/eq. The content of the following epoxy resin is not particularly limited, but when the epoxy resin (A) in the resin composition is 100% by mass, it is preferably 98% by mass or less, more preferably 95% by mass or less, especially preferably is 92% by mass or less. (A) Epoxy equivalent weight of (A-2) in epoxy resin: 200 g/eq. The lower limit of the content of the epoxy resin below is not particularly limited, but from the viewpoint of more significantly obtaining the desired effect of the present invention, when the epoxy resin (A) in the resin composition is 100% by mass, it is preferably 10% by mass. or more, more preferably 30 mass% or more, further preferably 40 mass% or more, even more preferably 50 mass% or more, and particularly preferably 60 mass% or more.

(A-2) epoxy equivalent in the resin composition: 200 g/eq. The mass ratio ((A-1) component/(A-2) component) of the specific epoxy resin (A-1) to the following epoxy resin is not particularly limited, but is preferably 0.005 or more, more preferably 0.01. or more, particularly preferably 0.05 or more. (A-2) epoxy equivalent in the resin composition: 200 g/eq. The upper limit of the mass ratio ((A-1) component/(A-2) component) of the specific epoxy resin (A-1) to the following epoxy resin is not particularly limited, but is preferably 5 or less, more preferably is 1 or less, particularly preferably 0.5 or less.

<(A-3) Other epoxy resins>

In the resin composition of the present invention, the epoxy resin (A) may further contain, as an optional component, another epoxy resin (A-3) that does not correspond to the component (A-1) and (A-2).

(A-3) It is preferable that other epoxy resins include epoxy resins having two or more epoxy groups in one molecule. (A-3) The ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the other epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, Particularly preferably, it is 70% by mass or more.

(A-3) Other epoxy resins include, but are not particularly limited to, cresol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthylene ether-type epoxy resin, naphthol novolac-type epoxy resin, and biphenyl-type epoxy resin. , naphthalene type epoxy resin, naphthol type epoxy resin, phenol aralkyl type epoxy resin, fluorene type epoxy resin, epoxy resin with a butadiene structure, ester type epoxy resin, etc.

(A-3) Specific examples of other epoxy resins include “N-690” manufactured by DIC (epoxy equivalent weight: 209 to 219 g/eq.) (cresol novolac type epoxy resin); “N-695” (epoxy equivalent weight 209 to 219 g/eq.) manufactured by DIC (cresol novolac type epoxy resin); “HP-7200” (epoxy equivalent weight: 254 to 264 g/eq.), “HP-7200HH” (epoxy equivalent weight: 274 to 286 g/eq.), and “HP-7200H” (epoxy equivalent weight: 272 to 284 g/eq.) manufactured by DIC. ), “HP-7200L” (epoxy equivalent weight 242 to 252 g/eq.) (dicyclopentadiene type epoxy resin); "EXA-7311" (epoxy equivalent weight 277 g/eq.) (naphthylene ether type epoxy resin) manufactured by DIC Corporation; “NC7000L” (epoxy equivalent weight 230 g/eq.) manufactured by Nippon Kayaku Co., Ltd. (naphthol novolac type epoxy resin); “NC3000H” (epoxy equivalent weight 291 g/eq.), “NC3000” (epoxy equivalent weight 280 g/eq.), “NC3000L” (epoxy equivalent weight 270 g/eq.), and “NC3100” (epoxy equivalent weight 258 g/eq.) manufactured by Nippon Kayaku Co., Ltd. .) (biphenyl type epoxy resin); “ESN475V” (epoxy equivalent weight 330 g/eq.) manufactured by Nittetsu Chemical & Materials Co., Ltd. (naphthalene type epoxy resin); “ESN485” (epoxy equivalent weight 270 g/eq.) manufactured by Nittetsu Chemical & Materials (naphthol type epoxy resin); “YX7700” (260 to 285 g/eq.) (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “PG-100” (epoxy equivalent weight: 260 g/eq.) and “CG-500” (epoxy equivalent weight: 310 g/eq.) manufactured by Osaka Gas Chemical Co., Ltd. (fluorene type epoxy resin); “JP-200” (epoxy equivalent weight 210 to 240 g/eq.) (epoxy resin with butadiene structure), “YX7800BH40” (epoxy equivalent weight 4,000 g/eq.), “YL7891BH30” (epoxy equivalent weight 8,000 g) manufactured by Nippon Soda Corporation. /eq.) (ester type epoxy resin). These may be used individually or in combination of two or more types.

(A-3) The epoxy equivalent of other epoxy resins is not particularly limited and is, for example, 15,000 g/eq. Below, 10,000g/eq. It may be as follows. The lower limit is, for example, 200 g/eq. It is excess. Epoxy equivalent weight is the mass of resin per equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(A-3) The weight average molecular weight (Mw) of the other epoxy resin is preferably 100 to 50,000, more preferably 200 to 30,000, and still more preferably 300 to 10,000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The content of the other epoxy resin (A-3) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably less than 50% by mass, more preferably 30% by mass. Hereinafter, more preferably 20 mass% or less, even more preferably 10 mass% or less, particularly preferably 5 mass% or less, the lower limit is, for example, 0 mass% or more, 0.1 mass% or more, 1 It may be more than mass %, etc.

The content of the other epoxy resin (A-3) in the (A) epoxy resin is not particularly limited, but when the epoxy resin (A) in the resin composition is 100% by mass, it is preferably 80% by mass or less, more preferably. Typically, it is 50 mass% or less, particularly preferably 30 mass% or less, and the lower limit thereof may be, for example, 0 mass% or more, 0.1 mass% or more, 1 mass% or more, or 10 mass% or more.

The content of (A) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 40% by mass or less, and further. Preferably it is 30 mass% or less, more preferably 20 mass% or less, and particularly preferably 15 mass% or less. The lower limit of the content of the (A) epoxy resin in the resin composition is not particularly limited, but is preferably 0.1 when the non-volatile component in the resin composition is 100% by mass from the viewpoint of more significantly obtaining the desired effect of the present invention. It is mass % or more, more preferably 0.5 mass % or more, further preferably 1 mass % or more, even more preferably 5 mass % or more, and particularly preferably 10 mass % or more.

<(B) Active ester compound>

The resin composition of the present invention contains (B) an active ester compound. (B) The active ester compound may be used individually, or two or more types may be used in combination in any ratio. (B) The active ester compound can have a function as an epoxy resin curing agent that reacts with and hardens the epoxy resin (A).

(B) Active ester compounds generally contain two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having these are preferably used. The active ester compound is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester compounds obtained from a carboxylic acid compound and a hydroxy compound are preferable, and active ester compounds obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. As phenol compounds or naphthol compounds, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, (B) the active ester compound includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and benzoyl phenol novolac. An active ester compound containing a cargo is preferable, and among these, it is more preferable that it is at least one type selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound, and a dicyclopentadiene type active ester compound is still more preferable. . As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.

(B) Commercially available active ester compounds include dicyclopentadiene-type diphenol structures, such as “EXB9451,” “EXB9460,” “EXB9460S,” “EXB-8000L,” and “EXB-8000L-65M.” ”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM”, (manufactured by DIC) ); As an active ester compound containing a naphthalene structure, “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-8150-60T”, “EXB-8150-62T”, and “EXB-9416-70BK” , “HPC-8150-60T”, “HPC-8150-62T”, “EXB-8” (manufactured by DIC); As a phosphorus-containing active ester compound, “EXB9401” (manufactured by DIC), as an active ester compound that is an acetylate of phenol novolak, “DC808” (manufactured by Mitsubishi Chemical Corporation), and as an active ester compound that is a benzoylate of phenol novolac, “YLH1026.” ", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "PC1300-02-65MA" (manufactured by Airwater Corporation) as an active ester compound containing a styryl group and a naphthalic structure.

(B) The active ester group equivalent of the active ester compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., and even more preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

The content of the active ester compound (B) in the resin composition is preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 5 mass%, when the non-volatile component in the resin composition is 100 mass%. % or more, particularly preferably 10 mass% or more. The upper limit of the content of the active ester compound (B) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass. Below, more preferably 30 mass% or less, even more preferably 25 mass% or less, particularly preferably 20 mass% or less.

The mass ratio of the active ester compound (B) to the epoxy resin (A) in the resin composition (component (B)/component (A)) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 1.0 or more. am. The upper limit of the mass ratio (component (B)/component (A)) of the active ester compound (B) to the epoxy resin (A) in the resin composition is preferably 5.0 or less, more preferably 3.0 or less, especially preferably It is less than 2.0.

<(B') Other hardeners>

The resin composition of the present invention may further contain (B') other curing agents other than component (B) as an optional component. (B') Other hardening agents may be used individually or in combination of two or more types. (B') Other curing agents, like the active ester compound (B), can have a function as an epoxy resin curing agent that reacts with and hardens the epoxy resin (A).

(B') Other curing agents are not particularly limited, but include, for example, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. A hardener may be mentioned. The resin composition of the present invention preferably contains a curing agent selected from phenol-based curing agents and carbodiimide-based curing agents, and particularly preferably contains a phenol-based curing agent.

As a phenol-based curing agent, a phenol-based curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenol-based curing agents include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd. ", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by Nittetsu Chemical & Materials Co., Ltd. ”, “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “TD” manufactured by DIC Corporation -2090-60M” and the like.

Examples of the carbodiimide-based curing agent include those having one or more, preferably two or more carbodiimide structures in one molecule, for example, tetramethylene-bis(t-butylcarbodiimide), Aliphatic biscarbodiimides such as cyclohexanebis(methylene-t-butylcarbodiimide); Biscabodiimides such as aromatic biscabodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(di Ethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly (methylenediphenylenecarbodiimide), and aromatic polycarbodiimide such as poly[methylenebis(methylphenylene)carbodiimide].

Commercially available carbodiimide-based curing agents include, for example, “CarbodiLite V-02B,” “CarbodyLite V-03,” “CarbodyLite V-04K,” and “CarbodyLite” manufactured by Nisshinbo Chemical Co., Ltd. V-07” and “Carbody Light V-09”; “Stabakusol P”, “Stabakusol P400”, and “Hycadyl 510” manufactured by Line Chemistry, etc. can be mentioned.

Examples of the acid anhydride-based curing agent include those having one or more acid anhydride groups in one molecule, and those having two or more acid anhydride groups in one molecule are preferred. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromelli anhydride. Triacic acid, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), and polymeric acid anhydrides such as styrene/maleic acid resin, which is a copolymerization of styrene and maleic acid. Commercially available acid anhydride-based curing agents include “HNA-100,” “MH-700,” “MTA-15,” “DDSA,” and “OSA” manufactured by Nippon Rika Corporation, and “YH-306” manufactured by Mitsubishi Chemical Corporation. , “YH-307”, “HN-2200”, “HN-5500” manufactured by Hitachi Kasei, “EF-30”, “EF-40”, “EF-60”, “EF-80” manufactured by Cray Vale. etc. can be mentioned.

Examples of the amine-based curing agent include those having at least one, preferably at least two amino groups in one molecule, and examples include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. , Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and a primary amine is more preferable. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobi Phenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane , 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( Examples include 4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine-based hardeners may be used, for example, "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S" manufactured by Nippon Kayaku Corporation, "KAYABOND C-100", "Kayahard A-A", and "Kaya". “Hard A-B”, “Kayahard A-S”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, etc.

Specific examples of benzoxazine-based curing agents include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemicals; “HFB2006M” manufactured by Showa Kobunshi Corporation; “P-d” and “F-a” manufactured by Shikoku Kasei Kogyo Co., Ltd. are included.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylenecyanate)), and 4,4'-methylenebis(2,6). -dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4) -cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Bifunctional cyanate resins such as cyanatephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazinated. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer in which the entire polymer is triazylated to form a trimer).

Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. You can.

(B') The reactor equivalent of the other curing agent is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., even more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. Reactor equivalent is the mass of curing agent per equivalent of reactor.

The content of (B') other curing agents in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, More preferably, it is 5 mass% or less, and particularly preferably, it is 3 mass% or less. The lower limit of the content of (B') other curing agents in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more. It may be more than % by mass, more than 1% by mass, more than 1.5% by mass, etc.

The content of the active ester compound (B) in the resin composition is preferably 10% by mass or more, more preferably 10% by mass or more, when the total of the active ester compound (B) and (B') other curing agents in the resin composition is 100% by mass. is 30% by mass or more, more preferably 40% by mass or more, particularly preferably 50% by mass or more.

<(C) Inorganic filler>

The resin composition of the present invention may further contain (C) an inorganic filler as an optional component. (C) The inorganic filler is contained in the resin composition in a particle state.

(C) As the material for the inorganic filler, an inorganic compound is used. (C) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Examples include barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Additionally, spherical silica is preferred as the silica. (C) Inorganic fillers may be used individually, or two or more types may be used in combination at any ratio.

(C) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Chemical Co., Ltd.; “SP60-05” and “SP507-05” manufactured by Shin-Ni-Tetsu Sumikin Materials, Inc.; “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C” manufactured by Adomatex Corporation; “UFP-30” manufactured by Denka Corporation; “Actual writing NSS-3N”, “Actual writing NSS-4N”, and “Actual writing NSS-5N” manufactured by Tokuyama Corporation; “SC2500SQ”, “SO-C4”, “SO-C2”, and “SO-C1” manufactured by Adomatex Corporation; “DAW-03” and “FB-105FD” manufactured by Denka Corporation; and the like.

(C) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, especially Preferably it is 0.7㎛ or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more. . (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the intermediate diameter can be measured as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial bottle and dispersing them by ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction type particle size distribution measuring device, set the light source wavelengths to blue and red, and measure the volume-based particle size distribution of the inorganic filler using a flow cell method. From the obtained particle size distribution, the median diameter is calculated. The average particle diameter was calculated as . Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Sesakusho Co., Ltd.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m2/g or more, more preferably 0.5 m2/g or more, further preferably 1 m2/g or more, especially preferably 3. It is more than ㎡/g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m2/g or less, more preferably 70 m2/g or less, further preferably 50 m2/g or less, especially preferably is less than 40㎡/g. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. there is.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned. In addition, one type of surface treatment agent may be used individually, and two or more types may be used in arbitrary combination.

Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., Shinetsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane couple) manufactured by Shinetsu Chemical Co., Ltd. ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.3% by mass by 0.3% by mass. It is more preferable that the surface is treated in an amount of 2 to 2% by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and even more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, 1.0 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Sesakusho, etc. can be used.

The content of the (C) inorganic filler in the resin composition is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, when the non-volatile component in the resin composition is 100% by mass. Preferably it is 85 mass% or less, especially preferably 80 mass% or less. The lower limit of the content of the (C) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 1% by mass or more, 10% by mass. % or more, and may be 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, especially preferably It is more than 70% by mass.

The mass ratio ((C) component/(A) component) of the (C) inorganic filler to the (A) epoxy resin in the resin composition is preferably 1 or more, more preferably 3 or more, and particularly preferably 5 or more. . The upper limit of the mass ratio ((C) component/(A) component) of the (C) inorganic filler to the (A) epoxy resin in the resin composition is preferably 30 or less, more preferably 20 or less, and particularly preferably 10. It is as follows.

<(D) Organic filler>

The resin composition of the present invention may further contain (D) an organic filler as an optional component.

(D) The organic filler exists in particulate form in the resin composition. (D) As the organic filler, it is preferable to use rubber particles from the viewpoint of significantly obtaining the desired effect of the present invention. (D) Organic fillers may be used individually, or two or more types may be used in combination at any ratio.

Examples of the rubber component contained in the rubber particles include silicone-based elastomers such as polydimethylsiloxane; Polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene Olefin-based thermoplastic elastomers such as copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene terpolymers, and ethylene-propylene-butene terpolymers; Thermoplastic elastomers, such as acrylic thermoplastic elastomers such as propyl poly(meth)acrylate, butyl poly(meth)acrylate, cyclohexyl poly(meth)acrylate, and octyl poly(meth)acrylate, are included. Additionally, silicone-based rubber such as polyorganosiloxane rubber may be mixed with the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower.

(D) The organic filler preferably contains core-shell type rubber particles from the viewpoint of significantly obtaining the desired effect of the present invention. A core-shell type rubber particle is a particulate organic filler consisting of a core particle containing the rubber component as exemplified above and one or more layers of shell portion covering the core particle. In addition, the core-shell type rubber particle is a core-shell type graft consisting of a core particle containing the rubber component as exemplified above and a shell portion obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. It is preferable that they are copolymer rubber particles. The core-shell type referred to here does not necessarily mean that the core particle and the shell portion are clearly distinguishable, but also includes those in which the boundary between the core particle and the shell portion is unclear, and the core particle does not need to be completely covered with the shell portion. .

The rubber component is preferably contained in the core-shell type rubber particles in an amount of 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. The upper limit of the content of the rubber component in the core-shell type rubber particle is not particularly limited, but is preferably, for example, 95% by mass or less, 90% by mass, from the viewpoint of sufficiently covering the core particle with the shell portion.

Monomer components forming the shell portion of the core-shell type rubber particles include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, ( (meth)acrylic acid esters such as glycidyl meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; Aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; It contains (meth)acrylonitrile, etc., and among these, it is preferable that it contains (meth)acrylic acid ester, and it is more preferable that it contains methyl (meth)acrylate.

Commercially available core-shell type rubber particles include, for example, “CHT” manufactured by Cheil Industries; “B602” manufactured by UMGABS; “Pararoid EXL-2602,” “Pararoid EXL-2603,” “Pararoid EXL-2655,” “Pararoid EXL-2311,” “Pararoid-EXL2313,” and “Pararoid EXL-” manufactured by Dow Chemical Japan. 2315", "Pararoid KM-330", "Pararoid KM-336P", "Pararoid KCZ-201", "Metablen C-223A", "Metablene E-901", and "Metablene" manufactured by Mitsubishi Rayon Corporation. Blen S-2001", "Metablen W-450A", "Metablen SRK-200", "Kaneace M-511", "Kaneace M-600", "Kaneace M-400", manufactured by Kaneka Corporation. Examples include “Kane Ace M-580” and “Kane Ace MR-01.”

(D) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 50 nm or more. (D) The upper limit of the average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 5,000 nm or less, more preferably 2,000 nm or less, and even more preferably 1,000 nm or less. (D) The average particle diameter (average primary particle diameter) of the organic filler can be measured using a zeta potential particle size distribution measuring device or the like.

The content of the (D) organic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further. Preferably it is 2% by mass or less. The lower limit of the content of the (D) organic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more and 0.01% by mass or more, It may be preferably 0.1 mass% or more, and more preferably 0.5 mass% or more.

<(E) Curing accelerator>

The resin composition of the present invention may further contain (E) a curing accelerator as an optional component. (E) The curing accelerator has the function of accelerating the curing of the (A) epoxy resin.

Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. The resin composition of the present invention preferably contains an amine-based curing accelerator or an imidazole-based curing accelerator, and particularly preferably contains an amine-based curing accelerator. (E) A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyrro. Mellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium Aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphonium tetraphenyl borate, tris (2-methyl aromatic phosphonium salts such as toxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of urea-based curing accelerators include 1,1-dimethylurea; Aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), aromatic dimethyl ureas such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], and the like.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Cylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s -Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and imidazole compounds and epoxy resins Adduct forms of .

As the imidazole-based curing accelerator, commercial products may be used, for example, "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemicals, and "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc. can be mentioned.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8. -Diazabicyclo(5,4,0)-undecene, etc. can be mentioned.

As the amine-based curing accelerator, a commercial product may be used, for example, “MY-25” manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

The content of the curing accelerator (E) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass or less, and further. Preferably it is 0.7 mass% or less, especially preferably 0.5 mass% or less. The lower limit of the content of the (E) curing accelerator in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.001% by mass or more, or 0.01% by mass. % or more, 0.1 mass% or more, etc.

<(F) Other additives>

The resin composition of the present invention may further contain arbitrary additives as non-volatile components. Examples of such additives include radically polymerizable compounds having a vinylphenyl group, (meth)acryloyl group, maleimide group, etc.; Radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; Thermosetting resins such as epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin, and epoxy resin; Thermoplastic resins such as polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; Organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improvers such as urea silane; Adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; Antioxidants such as hindered phenol antioxidants; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Phosphorus-based flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide), etc. flame retardants; Dispersants such as phosphoric acid ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; Stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers can be mentioned. (F) Other additives may be used individually, or two or more types may be used in combination at any ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

<(G) Organic solvent>

The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile component described above. (G) As the organic solvent, known solvents can be appropriately used, and the type is not particularly limited. (G) Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; Ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; Sulfoxide-based solvents such as dimethyl sulfoxide; Nitrile-based solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (G) Organic solvents may be used individually, or two or more types may be used in combination at any ratio.

In one embodiment, the content of the organic solvent (G) is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less, and 30% by mass. % or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, etc.

<Method for producing resin composition>

The resin composition of the present invention is, for example, in an optional preparation container, (A) an epoxy resin, (B) an active ester compound, (B') other curing agents, if necessary, (C) an inorganic filler, if necessary. Accordingly, (D) organic filler, optionally (E) curing accelerator, optionally (F) other additives, and optionally (G) organic solvent are added and mixed in any order and/or in part or all at the same time. It can be manufactured. Additionally, in the process of adding and mixing each component, the temperature may be appropriately set, and may be heated and/or cooled temporarily or over time. Additionally, during or after the addition and mixing process, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device. Additionally, degassing may be performed simultaneously with stirring or shaking under low pressure conditions such as under vacuum.

<Characteristics of resin composition>

The resin composition of the present invention includes (A) an epoxy resin and (B) an active ester compound, and (A) the epoxy resin is represented by (A-1) Chemical Formula 1, and has an epoxy equivalent weight of 1,000 g/eq. to 5,000. g/eq. of epoxy resin and (A-2) epoxy equivalent weight of 200 g/eq. It includes the following epoxy resins. By using such a resin composition, the dielectric loss tangent can be suppressed to a lower level, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with excellent copper plating peel strength can be obtained.

The cured product of the resin composition of the present invention may have the characteristic of low dielectric loss tangent (Df). Therefore, in one embodiment, for example, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 23°C as in Test Example 1 below is preferably 0.0200 or less, 0.0100 or less, or more. Preferably it is 0.0080 or less, 0.0070 or less, 0.0060 or less, more preferably 0.0050 or less, 0.0040 or less, 0.0035 or less, particularly preferably 0.0032 or less, 0.0030 or less.

The cured product of the resin composition of the present invention can have the characteristic of excellent copper plating peel strength. Therefore, in one embodiment, for example, as in Test Example 2 below, a copper plating conductor layer is formed on a cured product, and the copper plating peel strength calculated from the load when the copper plating conductor layer is peeled in the vertical direction is , preferably 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, even more preferably 0.3 kgf/cm or more, 0.35 kgf/cm or more, particularly preferably 0.4 kgf/cm or more, 0.45 kgf/cm or more. It could be more than that. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less.

The cured product of the resin composition of the present invention may have characteristics that can suppress the occurrence of cracks after desmear treatment. Therefore, in one embodiment, after manufacturing and desmearing a circuit board as in Test Example 3 below, when 100 copper pad portions of the circuit board are observed, the number of cracks may preferably be 10 or less.

<Use of resin composition>

The resin composition of the present invention can be suitably used as a resin composition for insulation purposes, particularly as a resin composition for forming an insulating layer. Specifically, it is suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. You can. In addition, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention is also widely used in applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealants, hole filling resins, and component filling resins. You can use it.

In addition, for example, when a semiconductor chip package is manufactured through the following processes (1) to (6), the resin composition of the present invention is used as a resin composition for a redistribution formation layer (cultivation layer) as an insulating layer for forming a redistribution layer. It can also be suitably used as a resin composition for forming a line forming layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a redistribution layer may be additionally formed on the sealing layer.

(1) A process of laminating a temporarily fixed film on a substrate,

(2) A process of temporarily fixing a semiconductor chip on a temporarily fixing film,

(3) Process of forming a sealing layer on the semiconductor chip,

(4) A process of peeling the base material and temporarily fixed film from the semiconductor chip,

(5) A process of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled, and

(6) A process of forming a redistribution layer as a conductor layer on the redistribution formation layer.

Additionally, since the resin composition of the present invention forms an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>

Although the resin composition of the present invention can be used by applying it in a varnish state, it is generally industrially suitable to use it in the form of a sheet-like laminate material containing the resin composition.

As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter abbreviated as “PEN”) ), polyester such as polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide ( PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.

Additionally, as the support, you may use a support with a release layer that has a release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Torres, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unichika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

In one embodiment, the resin sheet may further include an arbitrary layer as needed. Examples of such an optional layer include a protective film similar to the support provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

For the resin sheet, for example, a liquid resin composition is prepared as is, or a resin varnish is prepared by dissolving the resin composition in an organic solvent, and this is applied on a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by:

Examples of the organic solvent include the same organic solvents described as components of the resin composition. Organic solvents may be used individually, or two or more types may be used in combination.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, but for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the boiling point is heated at 50°C to 150°C for 3 minutes. A resin composition layer can be formed by drying for 10 minutes.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it becomes usable by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10㎛ or more.

Prepreg can be manufactured by known methods such as hot melt method and solvent method.

The thickness of the prepreg can be within the same range as that of the resin composition layer in the resin sheet.

The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). It can be used appropriately.

<Printed wiring board>

The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet.

(I) A process of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate.

(II) Process of curing (e.g., heat curing) the resin composition layer to form an insulating layer

The “inner layer substrate” used in step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate on which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an “inner layer circuit board.” Additionally, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the "inner layer substrate" referred to in the present invention. If the printed wiring board is a circuit board with embedded components, an inner layer board with embedded components may be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of members for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as “heat-pressing members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-compression member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can be preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization laminator manufactured by Meiki Sesakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurized laminator.

After lamination, the laminated resin sheets may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a heat-pressing member from the support side. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-mentioned lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

The support may be removed between step (I) and step (II), or may be removed after step (II).

In step (II), the resin composition layer is cured (for example, heat cured) to form an insulating layer made of a cured resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions normally employed when forming the insulating layer of a printed wiring board may be used.

For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, etc., but in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C. Preferably it is 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer is cured at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more. Preheating may be performed preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be additionally performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Additionally, when the support is removed after step (II), the removal of the support may occur between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). It can be done in between. Additionally, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg. The manufacturing method is basically the same as when using a resin sheet.

Process (III) is a process of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined appropriately according to the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. Usually, in this step (IV), removal of smear is also performed. The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

The swelling liquid used in the roughening treatment is not particularly limited, and includes an alkaline solution and a surfactant solution, and is preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid of 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan.

In addition, as the neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and examples of commercial products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

Treatment with a neutralizing liquid can be performed by immersing the treated surface that has been roughened with an oxidizing agent in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing an object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit, but it is preferably 0.5 nm or more, and more preferably 1 nm or more. Moreover, in one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium A layer formed of an alloy) may be mentioned. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable. desirable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full additive method, and from the viewpoint of ease of manufacturing, the semi-additive method can be used. It is preferable to form it by the Tiv method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

In another embodiment, the conductor layer may be formed using metal foil. When forming a conductor layer using metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the subtractive method and the modified semiadditive method.

Metal foil can be manufactured by known methods such as electrolysis and rolling, for example. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nikko Nisseki Kinzoku Corporation, 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Kozan Corporation.

<Semiconductor device>

The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trams, ships, aircraft, etc.). there is.

Example

Hereinafter, the present invention will be specifically explained by examples. The present invention is not limited to these examples. In addition, in the following, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. If there is no specific temperature designation, the temperature condition is room temperature (23°C). If there is no specific pressure designation, the pressure condition is normal pressure (1 atm).

<Synthesis Example 1: Synthesis of epoxy resin A>

According to the method described in Example 1-1 of Japanese Patent Application Laid-Open No. 2016-89165, 3,3',5,5'-tetramethyl-4,4'-biphenol diglycidyl ether and 4,4 Epoxy resin A was synthesized by reacting '-diacetoxybiphenyl in cyclohexanone and methyl ethyl ketone in the presence of N,N'-dimethylaminopyridine. The main component of epoxy resin A is an epoxy resin represented by Formula 1, Ar is a group represented by Formula X-1-1 or a group represented by Formula X-2-1, and is also represented by Formula X-1-1 It is an epoxy resin that alternately contains Ar, a group represented by the formula X-2-1, and Ar, and the epoxy equivalent weight is 1,900 g/eq.

<Example 1>

1 part of epoxy resin A (epoxy equivalent weight 1,900 g/eq.), bisphenol type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials, mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight 170 g /eq.) 5 parts, naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC, epoxy equivalent weight 144 g/eq.), 5 parts, active ester curing agent (“HPC-8150-62T” manufactured by DIC, non-volatile) 26 parts of toluene solution containing 62% by mass of components, active ester group equivalent of 234 g/eq.), 26 parts of inorganic filler (spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (Adomatex Co., Ltd.) Manufactured, “SO-C2”, average particle diameter 0.5㎛, specific surface area 5.8㎡/g) 72 parts, organic filler (manufactured by DOW, “EXL-2655”) 1 part, curing accelerator (manufactured by Wako Pure Chemical Industries, Ltd., 4 -Dimethylaminopyridine) 0.3 parts, MEK 10 parts, and toluene 10 parts were mixed and uniformly dispersed using a high-speed rotating mixer to prepare a resin composition (resin varnish).

<Example 2>

The amount of bisphenol-type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed to 5 parts. The resin composition ( Resin varnish) was prepared.

<Example 3>

The amount of bisphenol-type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed to 5 parts. In the same manner as in Example 1, except that 4 parts were changed and 3 parts of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nittetsu Chemical & Materials, epoxy equivalent weight 330 g/eq.) was added. , a resin composition (resin varnish) was prepared.

<Example 4>

The amount of bisphenol-type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed to 5 parts. was changed to 4 parts, and 3 parts of biphenyl skeleton epoxy resin (“NC-3000L” manufactured by Nippon Kayaku, epoxy equivalent weight 272 g/eq.) was added, and an activated ester curing agent (“HPC-8150-62T” manufactured by DIC) was added. ") was changed from 26 parts to 22.6 parts, and additionally 1-methoxy-2- of cresol novolac resin ("LA-3018-50P" manufactured by DIC, hydroxyl equivalent weight 151 g/eq., non-volatile matter 50%) A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 4 parts of propanol solution was added.

<Example 5>

The amount of bisphenol-type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed to 5 parts. was changed to 4 parts, and 3 parts of biphenyl skeleton epoxy resin (“NC-3000L” manufactured by Nippon Kayaku, epoxy equivalent weight 272 g/eq.) was added, and an activated ester curing agent (“HPC-8150-62T” manufactured by DIC) was added. ") was changed from 26 parts to 22.6 parts, and 3.3 parts of phenol novolac resin ("LA-1356" manufactured by DIC, hydroxyl equivalent 146 g/eq., MEK solution with 60% non-volatile matter) was added. Other than that, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

<Comparative Example 1>

Epoxy resin A was not used, and instead, another epoxy resin (“YX7800BH40” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight of 4,000 g/eq., cyclohexanone/MEK mixed solution with 40% non-volatile content, 3,3’,5 A resin composition (resin varnish) was prepared in the same manner as in Example 2, except that 2.5 parts of 5'-tetramethyl-4,4'-biphenol diglycidyl ether and biscresol fluorene (reaction product) was added. was prepared.

<Comparative Example 2>

Except that epoxy resin A was not used, and instead, 3.3 parts of another epoxy resin (“YL7891BH30” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 8000 g/eq., cyclohexanone/MEK mixed solution with 30% non-volatile content) was added. In the same manner as in Example 2, a resin composition (resin varnish) was prepared.

<Comparative Example 3>

Instead of using a bisphenol-type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials Co., Ltd.), and additionally without using a naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC Co., Ltd.), A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 10 parts of biphenyl skeleton epoxy resin (“NC-3000L” manufactured by Nippon Kayaku Co., Ltd.) was added.

<Comparative Example 4>

The amount of naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed from 5 parts to 8 parts, and additionally, 5 parts of biphenyl skeleton epoxy resin (“NC-3000L” manufactured by Nippon Kayaku Corporation) was added. , an active ester curing agent (“HPC-8150-62T” manufactured by DIC) was not used, and additionally, a cresol novolak resin (“LA-3018-50P” manufactured by DIC, hydroxyl equivalent weight 151, non-volatile matter 50% of 1 A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 16 parts of -methoxy-2-propanol solution) was added.

<Test Example 1: Measurement of dielectric loss tangent (Df)>

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) with a release layer was prepared. On the release layer of the support, the resin composition (resin varnish) prepared in Examples and Comparative Examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

The obtained resin sheet was heated at 190°C for 90 minutes to heat-cure the resin composition layer. After that, the support was peeled off to obtain a cured product of the resin composition. The cured product was cut into test pieces with a width of 2 mm and a length of 80 mm. For the above test piece, the dielectric loss tangent (Df) was measured by cavity resonance perturbation using “HP8362B” manufactured by Agilent Technologies, Inc. at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were made on three test pieces.

<Test Example 2: Measurement of copper plating peel strength>

(1) Base processing of inner layer circuit board

As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) having inner layer circuits (copper foil) on both sides was prepared. Both sides of the inner-layer circuit board were etched by 1 μm with “CZ8101” manufactured by Mack Co., Ltd. to roughen the copper surface.

(2) Laminate of resin sheets

The resin sheet obtained in Test Example 1 was laminated on both sides of the inner layer circuit board using a batch vacuum pressure laminator (two-stage build-up laminator, CVP700, manufactured by Nikko Materials). The laminate was performed so that the resin composition layer of the resin sheet was in contact with the inner layer circuit board. In addition, the laminate was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less and pressing it at 130°C and a pressure of 0.74 MPa for 45 seconds. Next, heat pressing was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Curing of the resin composition

The laminated resin sheet and inner layer circuit board were heated at 130°C for 30 minutes, and then heated at 170°C for 30 minutes to cure the resin composition to form an insulating layer. Thereafter, the support was peeled off to obtain a laminated board including an insulating layer, an inner layer circuit board, and an insulating layer in this order.

(4) Harmonization processing

The laminated substrate was immersed in a swelling liquid (Swelling Deep Securigant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by Atotech Japan) at 60°C for 10 minutes. Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P (aqueous solution of KnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan) at 80°C for 20 minutes. After that, the laminated substrate was was immersed in a neutralizing liquid (Reduction Soleucine Securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 40°C. Thereafter, the laminated substrate was dried at 80°C for 30 minutes and designated as an “evaluation substrate.” I got 'A'.

(5) Plating using semi-additive method

Evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After that, annealing was performed by heating at 150°C for 30 minutes. After that, an etching resist was formed and a pattern was formed by etching. After that, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, annealing was performed at 190°C for 60 minutes to obtain “Evaluation Board B.”

(6) Measurement of copper plating peel strength

In the conductor layer of evaluation board B, a cut was formed surrounding a rectangular portion with a width of 10 mm and a length of 100 mm. One end of the rectangular portion was peeled off and pinched with a clamping tool (Autocom type tester “AC-50C-SL” manufactured by TS Corporation). The rectangular portion was peeled in the vertical direction at room temperature at room temperature using a tool, and the load (kgf/cm) upon peeling 35 mm was measured as the copper plating peel strength.

<Test Example 3: Evaluation of cracks after desmearing>

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) with a release layer was prepared. On the release layer of the support, the resin composition (resin varnish) prepared in Examples and Comparative Examples was uniformly applied so that the thickness of the resin composition layer after drying was 25 μm. Thereafter, the resin varnish was dried at 80°C to 100°C (average 90°C) for 2.5 minutes to obtain a resin sheet including a support and a resin composition layer.

The resin sheet with a thickness of 25 ㎛ obtained above was formed into a core material (“E705GR” manufactured by Hitachi Kaseiko Co., Ltd.) in which circular copper pads (35 ㎛ copper thickness) with a diameter of 350 ㎛ were formed in a lattice shape at 400 ㎛ intervals to achieve a drift rate of 60%. , thickness of 400 μm) was laminated on both sides of the inner layer substrate using a batch-type vacuum pressurized laminator (two-stage build-up laminator “CVP700” manufactured by Nikko Materials) so that the resin composition layer was bonded to the inner layer substrate. The laminate was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then compressing it at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. This was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes. Additionally, the support layer was peeled off, and the obtained circuit board was immersed in Swelling Deep Securigant P from Atotech Japan Co., Ltd., a swelling liquid, at 60°C for 10 minutes. Next, it was immersed in Atotech Japan Co., Ltd.'s Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L), which is a roughening solution, at 80°C for 30 minutes. Finally, it was immersed in Atotech Japan Co., Ltd.'s reduction solution Securigant P, a neutralizing liquid, at 40°C for 5 minutes. 100 copper pad portions of the circuit board after the roughening treatment were observed to confirm the presence or absence of cracks in the resin composition layer. If there were 10 or less cracks, it was designated as “○”, and if there were more than 10 cracks, it was designated as “×”.

The content of non-volatile components in the resin compositions of Examples and Comparative Examples, the measurement results and evaluation results of Test Examples are shown in Table 1 below.

As shown in Table 1, in Comparative Example 4, which contains (A-1) a specific epoxy resin but does not contain (B) an active ester compound, the dielectric loss tangent is relatively high. In Comparative Example 3 using (A-1) a specific epoxy resin and (B) an active ester compound, dielectric loss tangent can be suppressed, but cracks tend to occur easily. (A-2) Epoxy equivalent weight is 200g/eq. In Comparative Example 2, which used an epoxy resin with a high epoxy equivalent weight having the structure represented by Formula 1 instead of the specific epoxy resin (A-1), together with the following epoxy resin and (B) an active ester compound, the occurrence of cracks was suppressed. However, the copper plating peel strength is low. Additionally, (A-2) has an epoxy equivalent weight of 200 g/eq. With the following epoxy resin and (B) active ester compound, (A-1) an epoxy equivalent of 1,000 g/eq instead of the specific epoxy resin. In Comparative Example 1 using an epoxy resin of 5,000 g/eq. to 5,000 g/eq., cracks tend to occur easily and the copper plating peel strength is low. In contrast, (A-2) the epoxy equivalent weight was 200 g/eq. When the resin composition of the present invention containing the specific epoxy resin (A-1) is used together with the following epoxy resins and (B) the active ester compound, these problems can be solved.

This application is based on Patent Application No. 2021-032681 (filing date: March 2, 2021) filed with the Japan Patent Office, and all contents thereof are included in this specification.

Claims (19)

A resin composition comprising (A) an epoxy resin and (B) an active ester compound,
(A) The component is,
(A-1) Formula 1:
[Formula 1]

[In Formula 1,
R ¹ each independently represents a hydrogen atom, an alkyl-carbonyl group which may have a substituent, an alkenyl-carbonyl group which may have a substituent, or an aryl-carbonyl group which may have a substituent, and at least one of R ¹ The above are groups selected from alkyl-carbonyl groups which may have a substituent, alkenyl-carbonyl groups which may have a substituent, and aryl-carbonyl groups which may have a substituent;
Ar is each independently, Formula X:
[Formula X]

(In formula
R ² and R ³ each independently represent a substituent;
X represents a single bond or an organic group;
a and b each independently represent 0, 1, 2, 3, or 4;
* indicates binding site)
Represents a group represented by;
n is an integer greater than or equal to 1 and represents the number of repeat units]
The epoxy equivalent weight, expressed as 1,000 g/eq. to 5,000 g/eq. of epoxy resin and
(A-2) Epoxy equivalent weight is 200g/eq. A resin composition containing the following epoxy resin. The method of claim 1, wherein Ar is each independently represented by Formula X-1:
[Formula X-1]

(In Formula X-1,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group;
X ¹ represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;
R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;
* indicates binding site)
A group represented by or formula X-2:
[Formula X-2]

(In Formula X-2,
X ² represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;
R ^x each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, or two ^R It forms a non-aromatic ring which may have;
* indicates binding site)
A resin composition comprising at least one group represented by Ar, and at least one group Ar represented by Formula X-1 and Ar represented by Formula X-2. The resin composition according to claim 2, wherein X ¹ and X ² are a single bond. The resin composition according to any one of claims 1 to 3, wherein the content of component (A-1) is 3% by mass to 20% by mass when the component (A) is 100% by mass. The method according to any one of claims 1 to 4, wherein the mass ratio of the (A-1) component to the (A-2) component ((A-1) component/(A-2) component) is 0.01 to 1. , resin composition. The resin composition according to any one of claims 1 to 5, wherein the content of component (A) is 1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 6, wherein the content of component (B) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 7, wherein the mass ratio of component (B) to component (A) (component (B)/component (A)) is 0.5 to 3.0. The resin composition according to any one of claims 1 to 8, further comprising (C) an inorganic filler. The resin composition according to claim 9, wherein component (C) is silica. The resin composition according to claim 9 or 10, wherein the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 11, further comprising (D) an organic filler. The resin composition according to claim 12, wherein component (D) contains core-shell type rubber particles. The resin composition according to any one of claims 1 to 13, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C. A cured product of the resin composition according to any one of claims 1 to 14. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 14. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 14 provided on the support. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor device comprising the printed wiring board according to claim 18.